Patent GB-670255-A (GB)
Title: Process for preparing sulphonyl derivatives of di-tertiary alkyl peroxides
IPC: C07C409/44
Filed: 1948-12-08
Abstract: Sulphonyl chlorides or bromides of di-tertiaryalkyl peroxides are prepared by reacting the peroxides with sulphur dioxide and chlorine or bromine in the presence of actinic light.  Reaction temperatures of from -25 DEG  C. up to 50 DEG  C. are employed. Preferably, the peroxides are reacted in excess over the sulphur dioxide and halogen, while the sulphur dioxide is normally employed in excess over the halogen to prevent excess of halogenation.  The reaction is generally carried out using a liquid peroxide; in the case of solid peroxides or where it is intended to effect polysulphohalogenation, the peroxide is diluted by or suspended in an inert solvent, e.g. carbon tetrachloride, chloroform or other polyhalogenated hydrocarbon.  The peroxides may be treated in vapour phase, normally under reduced pressure. The ditertiary-alkyl peroxides preferably have a plurality of alpha-methyl groups and not more than 12 carbon atoms. Di-tertiary butyl peroxide and its chloro and bromo derivatives and di-tertiary-amyl, tertiary-butyl tertiary-amyl, tertiary - butyl beta, beta - dibromo - tertiary - amyl, di-tertiary-hexyl, tertiary-hexyl tertiary-heptyl, di-tertiary-heptyl, di-tertiary-octyl and di-tertiary-nonyl peroxides are mentioned. The sulphonyl halides may be converted into other sulphonyl derivatives by replacement of the halogen by a polar group by reaction with a hydrogen active compound, namely a polar compound containing a replaceable hydrogen atom directly attached to a nitrogen or oxygen atom, e.g. metal hydroxides, water, alcohols, ammonia, amines and organic hydroperoxides.  In examples: (1) di-tertiary-butyl peroxide is treated with a gaseous mixture of sulphur dioxide and chlorine at between 6-8 DEG  C., while illuminated by a lamp and 2-tertiary-butylperoxy-2-methyl propane sulphonyl chloride is isolated by stripping-off the volatiles and distilling under reduced pressure; (2) 2-tertiarybutylperoxy - 2 - methyl hexane is similarly treated at below about 50 DEG  C. with gaseous sulphur dioxide and bromine to yield the product C11H23O4SBr; (3) di-tertiary-hexyl peroxide in carbon tetrachloride is treated as in (1) with excess of sulphur dioxide and chlorine yielding a product C12H26-nO2(SO2Cl)n, where n is greater than 1; (4) bromo-di-tertiary-butyl peroxide is reacted as in (1) at below about 20 DEG  C. to yield a product C8H16O4SClBr; (5) the sulphonyl chloride obtained as in (1) is treated with aqueous KOH to form the corresponding potassium sulphonate; or (6) with excess of calcium hydroxide to form the mono- and dicalcium sulphonates; (7) the potassium salt of (5) is treated with hydrochloric acid in aqueous solution yielding, on cooling, white crystals of the free sulphonic acid; (8) the reaction mixture obtained as in (2) is directly hydrolysed by addition of water and the free sulphonic acid separated after ethereal extraction of the product; (9) the reaction mixture obtained as in (1) is stripped of volatiles and reacted with aniline to form the corresponding sulphonanilide; (10) the crude product obtained as in (1) is poured into concentrated ammonia containing ice and yields the sulphonamide; or (11) is shaken with excess aqueous NaOH containing di-n-butylamine, so yielding the N,N-dibutyl sulphonamide; (12) the stripped product obtained as in (1) is heated in ether at 10 DEG  C. with sodium tertiary-butyl hydroperoxide yielding a new product, tertiary-butyl 2-tertiary-butyl peroxy-2-methyl-propane per sulphonate.  The Specification as open to inspection under Sect. 91 is not restricted to the use of actinic light in the sulphohalogenation and refers to sulphonyl derivatives obtained by replacing the halogen of the sulphonyl halides by any monovalent group; organic acids are given as a further example of hydrogen active compounds. This subject-matter does not appear in the Specification as accepted.